Alkylated anisole-containing lubricating oil base stocks and processes for preparing the same

ABSTRACT

Compounds having the formula (F-I) below are provided herein: 
                         
wherein R 1  and R 2  at each occurrence are independently a C 1 -C 5000  alkyl group; R 3  at each occurrence is independently hydrogen or a C 1 -C 5000  alkyl group; R 4  is a C 1 -C 50  alkyl group or an unsubstituted or substituted phenyl group; R 5  at each occurrence is independently hydrogen or a C 1 -C 30  alkyl group; n is 1, 2, 3, or 4; and m+n is 5. Processes for preparing compounds of formula (F-I) as well as base stock and lubricant compositions containing compounds of formula (F-I) are also provided.

PRIORITY CLAIMS

This application is a divisional application of U.S. application SerialNo. 15/830,484 filed Dec. 4, 2017, now U.S. Pat. No. 10,774,282, whichclaims the benefit of United States Provisional Application No.62/446,933, filed Jan. 17, 2017; U.S. Provisional Application No.62/439,653, filed Dec. 28, 2016 (2016EM350); and U.S. ProvisionalApplication No. 62/439,660, filed Dec. 28, 2016 (2016EM351), thedisclosures of which are incorporated by reference herein in theirentirety.

FIELD OF THE INVENTION

This disclosure relates to alkylated anisole compounds, processes forproducing the alkylated anisole compounds, and lubricating oil basestocks and lubricating oils including the alkylated anisole compounds.

BACKGROUND OF THE INVENTION

Lubricants in commercial use today are prepared from a variety ofnatural and synthetic base stocks admixed with various additive packagesand solvents depending upon their intended application. Trends inautomotive and industrial lubrication require formulations to achieveimproved energy and fuel efficiency as well as greater stability. Toachieve improved energy efficiency may require use of base stocks withlower viscosity, improved friction and lower traction. Although, at thesame time, base stocks must also remain durable in increasingly severeconditions including high temperature and high workloads. Further, it isdesirable that base stocks resist chemical degradation from commonenvironmental elements, such as oxygen and water.

One category of base stocks, Group V base stocks, which are syntheticbase stocks, find application in automotive and industrial lubricantformulations. Examples of Group V base stocks include esters, alkylatedaromatics (e.g., alkylated naphthalenes), and polyalkylene glycols(PAGs). Group V base stocks are often incorporated into lubricantformulations to improve the solubility of additives, improve depositperformance, reduce volatility, and/or enhance the thermal-oxidativestability of the lubricant. However, it is difficult for a base stock tohave a combination of such desirable properties. For example, esters arepolar base stocks that help solubilize additives in hydrocarbon basestocks. However, esters may be susceptible to hydrolytic break down.Further, due to their high polarity, esters may interfere with ananti-wear additive's ability to interact with metal surfaces, therebylimiting esters' efficacies. Additionally, the polarity of esters canalso cause incompatibilities with elastomer seals.

As another example, alkylated aromatics, particularly alkylatednaphthalenes, have high oxidative stability. However, since alkylatednaphthalenes are less polar than esters, they are not as capable asesters in solubilizing additives in the hydrocarbon base stocks.Furthermore, alkylated naphthalenes may have high pour points resultingin poor low temperature fluidity.

Therefore, there is a need for synthetic base stocks that can achieve acombination of desirable properties, including but not limited to: 1)improved low temperature fluidity, 2) low volatility, 3) highthermal-oxidative stability, and 4) low viscosity.

SUMMARY OF THE INVENTION

It has been found that alkylated anisoles having enhanced lowtemperature fluidity, low volatility, high thermal and oxidativestability as well as low viscosity can be achieved by contacting ananisole-derivative compound with an unhydrogenated polyalpha-olefin(uPAO) in the presence of an acid catalyst.

Thus, this disclosure relates in part to a compound having the formula(F-I) below:

wherein R¹ and R² at each occurrence are independently a C₁-C₅₀₀₀ alkylgroup; R³ at each occurrence is independently hydrogen or a C₁-C₅₀₀₀alkyl group; R⁴ is a C₁-C₅₀ alkyl group or an unsubstituted orsubstituted phenyl group; R⁵ at each occurrence is independentlyhydrogen or a C₁-C₃₀ alkyl group; n is 1, 2, 3, or 4; and m+n is 5.

This disclosure also relates in part to a process for making a compoundof formula (F-I), the process comprising reacting a compound having thefollowing formula (F-Ia):

with an olefin-containing material comprising a compound having thefollowing formula (F-Ib):

in the presence of an acid catalyst.

This disclosure yet further relates in part to a lubricant base stockcomprising one or more of the compounds of formula (F-I).

This disclosure further relates in part to a formulated lubricantcomprising one or more of the lubricant base stocks described herein.

Other embodiments, including particular aspects of the embodimentssummarized above, will be evident from the detailed description thatfollows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates ¹H NMR spectra of Product I in the Examples of thisdisclosure.

FIG. 2 illustrates ¹³C NMR spectra of Product I.

FIG. 3 illustrates gas chromatography (GC) spectra of Product I.

FIG. 4 illustrates ¹H NMR spectra of Product II in the Examples of thisdisclosure.

FIG. 5 illustrates ¹³C NMR spectra of Product II.

FIG. 6 illustrates GC spectra of Product II.

FIGS. 7a and 7b illustrate a traction curve and a Stribeck curve,respectively, for Product I.

FIGS. 8a and 8b illustrate a traction curve and a Stribeck curve,respectively, for Synesstic™ 5.

FIGS. 9a and 9b illustrate a traction curve and a Stribeck curve,respectively, for Esterex™ NP343.

DETAILED DESCRIPTION OF THE INVENTION

In various aspects of the invention alkylated anisole compounds offormula F-I, processes for producing the alkylated anisole compounds,and lubricating oil base stocks and lubricating oils including thealkylated anisole compounds are provided herein.

I. Definitions

For purposes of this invention and the claims hereto, the numberingscheme for the Periodic Table Groups is according to the IUPAC PeriodicTable of Elements as of Jan. 1, 2017.

The term “and/or” as used in a phrase such as “A and/or B” herein isintended to include “A and B”, “A or B”, “A”, and “B”.

The terms “substituent”, “radical”, “group”, and “moiety” may be usedinterchangeably.

As used herein, and unless otherwise specified, the term “C” meanshydrocarbon(s) having n carbon atom(s) per molecule, wherein n is apositive integer.

As used herein, and unless otherwise specified, the term “hydrocarbon”means a class of compounds containing hydrogen bound to carbon, andencompasses (i) saturated hydrocarbon compounds, (ii) unsaturatedhydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds(saturated and/or unsaturated), including mixtures of hydrocarboncompounds having different values of n.

As used herein, and unless otherwise specified, the term “alkyl” refersto a saturated hydrocarbon radical having from 1 to 1000 carbon atoms(i.e. C₁-C₁₀₀₀ alkyl). Examples of alkyl groups include, but are notlimited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,decyl, and so forth. The alkyl group may be linear, branched or cyclic.“Alkyl” is intended to embrace all structural isomeric forms of an alkylgroup. For example, as used herein, propyl encompasses both n-propyl andisopropyl; butyl encompasses n-butyl, sec-butyl, isobutyl and tert-butyland so forth. As used herein, “C₁ alkyl” refers to methyl (—CH₃), “C₂alkyl” refers to ethyl (—CH₂CH₃), “C₃ alkyl” refers to propyl(—CH₂CH₂CH₃) and isopropyl, and “C₄ alkyl” refers to the butyl groups(e.g. —CH₂CH₂CH₂CH₃, —CH(CH₃)CH₂CH₃, —CH₂CH(CH₃)₂, etc.). Further, asused herein, “Me” refers to methyl, “Et” refers to ethyl, “i-Pr” refersto isopropyl, “t-Bu” refers to tert-butyl, and “Np” refers to neopentyl.

As used herein, and unless otherwise specified, the term “aromatic”refers to unsaturated hydrocarbons comprising an aromatic ring instructures thereof, the aromatic ring having a delocalized conjugated πsystem and preferably having from 4 to 20 carbon atoms. Exemplaryaromatics include, but are not limited to, benzene, toluene, xylenes,mesitylene, ethylbenzenes, cumene, naphthalene, methylnaphthalene,dimethylnaphthalenes, ethylnaphthalenes, acenaphthalene, anthracene,phenanthrene, tetraphene, naphthacene, benzanthracenes, fluoranthrene,pyrene, chrysene, triphenylene, and the like, and combinations thereof.The aromatic may optionally be substituted, e.g., with one or more alkylgroup, alkoxy group, halogen, etc. The aromatic ring may comprise one ormore heteroatoms. Examples of heteroatoms include, but are not limitedto, nitrogen, oxygen, and/or sulfur. Aromatics with one or moreheteroatom in the aromatic ring therein include, but are not limited tofuran, benzofuran, thiophene, benzothiophene, oxazole, thiazole and thelike, and combinations thereof. The aromatic ring may be monocyclic,bicyclic, tricyclic, and/or polycyclic (in some embodiments, at leastmonocyclic rings, only monocyclic and bicyclic rings, or only monocyclicrings) and may take the form of fused rings.

As used herein, the term “olefin” refers to an unsaturated hydrocarboncompound having a hydrocarbon chain containing at least onecarbon-to-carbon double bond in the structure thereof, wherein thecarbon-to-carbon double bond does not constitute a part of an aromaticring. The olefin may be straight-chain, branched-chain or cyclic.“Olefin” is intended to embrace all structural isomeric forms ofolefins, unless it is specified to mean a single isomer or the contextclearly indicates otherwise.

As used herein, the term “alpha-olefin” refer to an olefin having aterminal carbon-to-carbon double bond ((R¹R²)—C═CH₂) in the structurethereof.

As used herein, “polyalpha-olefin(s)” (“PAO(s)”) includes anyoligomer(s) and polymer(s) of one or more alpha-olefin monomer(s). Thus,the PAO can be a dimer, a trimer, a tetramer, or any other oligomer orpolymer comprising two or more structure units derived from one or morealpha-olefin monomer(s). The PAO molecule can be highly regio-regular,such that the bulk material exhibits an isotacticity, or asyndiotacticity when measured by ¹³C NMR. The PAO molecule can be highlyregio-irregular, such that the bulk material is substantially atacticwhen measured by ¹³C NMR. A PAO material made by using ametallocene-based catalyst system is typically called a metallocene-PAO(“mPAO”), and a PAO material made by using traditionalnon-metallocene-based catalysts (e.g., Lewis acids, supported chromiumoxide, and the like) is typically called a conventional PAO (“cPAO”).

A PAO molecule as obtained from the polymerization or oligomerization ofalpha-olefin monomers, without further hydrogenation thereof, typicallycontains an ethylenically unsaturated C═C double bond in the structurethereof. An unhydrogenated PAO is sometimes referred to as a “uPAO”herein. A uPAO material could comprise, among others, vinyls (F-A below,where R is an alkyl), 2,2-di-substituted olefins (F-B below,also-known-as vinylidenes, where R¹ and R², the same or different, arealkyl groups), 1,2-di-substituted olefins (including the E- andZ-isomers of F-C1 and F-C2 below, also-known-as di-substitutedvinylenes, where R¹ and R², the same or different, are alkyl groups),and tri-substituted olefins (F-D below, also-known-as tri-substitutedvinylenes, where R¹, R², and R³, the same or different, are alkylgroups). The vinyls and vinylidenes are terminal olefins, while the di-and tri-substituted vinylene olefins are internal olefins.

A uPAO can be partially or substantially completely hydrogenated in thepresence of hydrogen and a hydrogenation catalyst to reduce theethylenic unsaturation thereof and thereby obtaining a hydrogenated PAO.Such hydrogenated PAO can be more stable compared to the correspondinguPAO, offering higher thermal and oxidative resistance. A uPAO can beotherwise chemically modified to obtain a derivative thereof given thechemical reactivity of the ethylenic C═C double bond therein. Thederivative can offer various interesting physical and chemicalproperties depending on the functional group attached to the carbonchain as a result of the modification.

As used herein, the term “lubricant” refers to a substance that can beintroduced between two or more moving surfaces and to lower the level offriction between two adjacent surfaces moving relative to each other. Alubricant “base stock” is a material, typically a fluid at the operatingtemperature of the lubricant, used to formulate a lubricant by admixingwith other components. Non-limiting examples of base stocks suitable inlubricants include API Group I, Group II, Group III, Group IV, Group Vand Group VI base stocks. PAOs, particularly hydrogenated PAOs, haverecently found wide use in lubricant formulations as Group IV basestocks.

NMR spectroscopy provides key structural information about thesynthesized polymers. Proton NMR (¹H-NMR) analysis of the uPAO gives aquantitative breakdown of the olefinic structure types (i.e., vinyls,1,2-di-substituted and tri-substituted vinylenes, and vinylidenes). Inthe present disclosure, compositions of mixtures of olefins comprisingterminal olefins (vinyls and vinylidenes) and internal olefins(1,2-di-substituted vinylenes and tri-substituted vinylenes) aredetermined by using ¹H-NMR. Specifically, a NMR instrument of at least a500 MHz is run under the following conditions: a 30° flip angle RFpulse, 120 scans, with a delay of 5 seconds between pulses; sampledissolved in CDCl₃ (deuterated chloroform); and signal collectiontemperature at 25° C. The following approach is taken in determining theconcentrations of the various olefins among all of the olefins from anNMR graph. First, peaks corresponding to different types of hydrogenatoms in vinyls (T1), vinylidenes (T2), 1,2-di-substituted vinylenes(T3), and tri-substituted vinylenes (T4) are identified at the peakregions in TABLE I below. Second, areas of each of the above peaks (A1,A2, A3, and A4, respectively) are then integrated. Third, quantities ofeach type of olefins (Q1, Q2, Q3, and Q4, respectively) in moles arecalculated (as A1/2, A2/2, A3/2, and A4, respectively). Fourth, thetotal quantity of all olefins (Qt) in moles is calculated as the sumtotal of all four types (Qt=Q1+Q2+Q3+Q4). Finally, the molarconcentrations (C1, C2, C3, and C4, respectively, in mol %) of each typeof olefin, on the basis of the total molar quantity of all of theolefins, is then calculated (in each case, Ci=100*Qi/Qt).

TABLE I Number Hydrogen Atoms of Quantity Concentration Type Olefin PeakRegion Peak Hydrogen of Olefin of Olefin No. Structure (ppm) Area Atoms(mol) (mol %) T1 CH₂ ═CH − R₁ 4.95-5.10 A1 2 Q1 = A1/2 C1 T2 CH₂ ═CR₁R₂4.70-4.84 A2 2 Q2 = A2/2 C2 T3 CHR₁═CHR₂ 5.31-5.55 A3 2 Q3 = A3/2 C3 T4CR₁R₂ ═CHR₃ 5.11-5.30 A4 1 Q4 = A4  C4

Carbon-13 NMR (¹³C-NMR) is used to determine tacticity of the PAOs ofthe present invention. Carbon-13 NMR can be used to determine theconcentration of the triads, denoted (m,m)-triads (i.e., meso, meso),(m,r)-(i.e., meso, racemic) and (r,r)-(i.e., racemic, racemic) triads,respectively. The concentrations of these triads defines whether thepolymer is isotactic, atactic or syndiotactic. In the presentdisclosure, the concentration of the (m,m)-triads in mol % is recordedas the isotacticity of the PAO material. Spectra for a PAO sample areacquired in the following manner. Approximately 100-1000 mg of the PAOsample is dissolved in 2-3 ml of chloroform-d for ¹³C-NMR analysis. Thesamples are run with a 60 second delay and 90° pulse with at least 512transients. The tacticity was calculated using the peak around 35 ppm(CH₂ peak next to the branch point). Analysis of the spectra isperformed according to the paper by Kim, I.; Zhou, J.-M.; and Chung, H.Journal of Polymer Science: Part A: Polymer Chemistry 2000, 381687-1697. The calculation of tacticity is mm*100/(mm+mr+rr) for themolar percentages of (m,m)-triads, mr*100/(mm+mr+rr) for the molarpercentages of (m,r)-triads, and rr*100/(mm+mr+rr) for the molarpercentages of (r,r)-triads. The (m,m)-triads correspond to 35.5-34.55ppm, the (m,r)-triads to 34.55-34.1 ppm, and the (r,r)-triads to34.1-33.2 ppm.

II. Alkylated Anisole Compounds Useful for Base Stocks

The present disclosure relates to alkylated anisole compounds, which areuseful in base stock compositions due to their increased thermal andoxidative stability, low volatility and viscosity as well as their goodlow temperature fluidity. In particular, alkylated anisole compounds areprovided herein, which can be selectively synthesized from a uPAO and ananisole-derivative compound such that the anisole-derivative compoundbonds predominately to a tertiary carbon of the uPAO. Thus, compoundshaving the formula (F-I) below are provided herein:

wherein R¹ and R² at each occurrence are independently a C₁-C₅₀₀₀ alkylgroup; R³ at each occurrence is independently hydrogen or a C₁-C₅₀₀₀alkyl group; R⁴ is a C₁-C₅₀ alkyl group or an unsubstituted orsubstituted phenyl group; R⁵ at each occurrence is independentlyhydrogen or a C₁-C₃₀ alkyl group; n is 1, 2, 3, or 4; and m+n is 5.

In some embodiments, n may be 2, 3, or 4. In such variations, where n is2, 3, or 4, each moiety comprising R¹, R², and R³ may be bonded to thephenyl moiety at any suitable location with respect to the —OR⁴ moiety,namely at a para (p-), meta (m-), or ortho (o-) position with respect tothe —O—R⁴ moiety. Further, where n is 2, 3 or 4, it is understood hereinthat each R¹, R², and R³ in each moiety may be the same or different.

In other embodiments, n may be 1. In such variations where n is 1, it isunderstood herein that the moiety comprising R¹, R², and R³ may bebonded to the phenyl moiety at any suitable location with respect to the—O—R⁴ moiety, namely at a para (p-), meta (m-), or ortho (o-) positionwith respect to the —O—R⁴ moiety. In particular, where n is 1, themoiety comprising R¹, R², and R³ may be bonded to the phenyl moiety at aposition para to the —O—R⁴ moiety.

In one embodiment, an R³ may be hydrogen, e.g., when a uPAO used duringsynthesis is a vinylidene olefin. In particular, where n is 1, R³ may behydrogen.

Alternatively, an R³ may be a C₁-C₅₀₀₀ alkyl group, a C₁-C₄₀₀₀ alkylgroup, a C₁-C₃₀₀₀ alkyl group, a C₁-C₂₀₀₀ alkyl group, a C₁-C₁₀₀₀ alkylgroup, a C₁-C₉₀₀ alkyl group, a C₁-C₈₀₀ alkyl group, a C₁-C₇₀₀ alkylgroup, a C₁-C₆₀₀ alkyl group, a C₁-C₅₀₀ alkyl group, a C₁-C₄₀₀ alkylgroup, a C₁-C₃₀₀ alkyl group, a C₁-C₂₀₀ alkyl group, a C₁-C₁₀₀ alkylgroup, a C₁-C₅₀ alkyl group, a C₁-C₃₀ alkyl group, or C₁-C₁₀ alkylgroup. The alkyl group may be linear or branched. In particular, an R³may be a C₁-C₁₀₀ alkyl group.

In certain aspects, where n is 1, R³ may be a C₁-C₅₀₀₀ alkyl group, aC₁-C₄₀₀₀ alkyl group, a C₁-C₃₀₀₀ alkyl group, a C₁-C₂₀₀₀ alkyl group, aC₁-C₁₀₀₀ alkyl group, a C₁-C₉₀₀ alkyl group, a C₁-C₈₀₀ alkyl group, aC₁-C₇₀₀ alkyl group, a C₁-C₆₀₀ alkyl group, a C₁-C₅₀₀ alkyl group, aC₁-C₄₀₀ alkyl group, a C₁-C₃₀₀ alkyl group, a C₁-C₂₀₀ alkyl group, aC₁-C₁₀₀ alkyl group, a C₁-C₅₀ alkyl group, a C₁-C₃₀ alkyl group, orC₁-C₁₀ alkyl group. Preferably, where n is 1, R³ may be a C₁-C₁₀₀ alkylgroup.

Additionally or alternatively, R¹ and R² at each occurrence eachindependently may be a C₁-C₅₀₀₀ alkyl group, a C₁-C₄₀₀₀ alkyl group, aC₁-C₃₀₀₀ alkyl group, a C₁-C₂₀₀₀ alkyl group, a C₁-C₁₀₀₀ alkyl group, aC₁-C₉₀₀ alkyl group, a C₁-C₈₀₀ alkyl group, a C₁-C₇₀₀ alkyl group, aC₁-C₆₀₀ alkyl group, a C₁-C₅₀₀ alkyl group, a C₁-C₄₀₀ alkyl group, aC₁-C₃₀₀ alkyl group, a C₁-C₂₀₀ alkyl group, a C₁-C₁₀₀ alkyl group, aC₁-C₅₀ alkyl group, a C₁-C₃₀ alkyl group, or C₁-C₁₀ alkyl group. Inparticular, R¹ and R² at each occurrence each independently may be aC₁-C₁₀₀ alkyl group. The alkyl group may be linear or branched.

In certain variations, R¹ and R² at each occurrence each independentlymay be a C₁-C₃₀₀ linear alkyl group, a C₁-Coo linear alkyl group, aC₁-C₅₀ linear alkyl group, a C₁-C₃₀ linear alkyl group or C₁-C₁₀ linearalkyl group. In a particular embodiment, R¹ and R² at each occurrencemay be the same or different and each independently may be a C₁-C₁₀₀linear alkyl group or a C₁-C₃₀ linear alkyl group.

In another embodiment, an R¹ may be a C₁-C₁₀₀ linear alkyl group, aC₁-C₅₀ linear alkyl group, a C₁-C₃₀ linear alkyl group or C₁-C₁₀ linearalkyl group and an R² may be a C₁-C₅₀₀ linear or branched alkyl group, aC₁-C₃₀₀ linear or branched alkyl group, a C₁-C₁₀₀ linear or branchedalkyl group, a C₁-C₅₀ linear or branched alkyl group, a C₁-C₃₀ linear orbranched alkyl group or a C₁-C₁₀ linear or branched alkyl group, e.g.,where a uPAO used during synthesis is formed from linear alpha-olefinsand a metallocene catalyst as further described herein. In particular,an R¹ may be a C₁-C₃₀ linear alkyl group and an R² may be a C₁-C₅₀₀linear or branched alkyl group.

In certain variations, where an R¹ or an R² may be a C₃-C₅₀₀₀ branchedalkyl group, an R² may have the following formula (F-II) below:

wherein: R⁶ and R⁷ at each occurrence are each independently a hydrogenor a C₁-C₃₀ linear alkyl group and k is a positive integer, providedhowever, among all of R⁶ and R⁷, at least one is a C₁-C₃₀ linear alkylgroup; and R⁸ is a hydrogen or a C₁-C₃₀ linear alkyl group. The positiveinteger, k, may be from 1 to 1000, 2 to 1000, 2 to 500, 2 to 100, 50 to500, 50 to 200, 2 to 50, or 2 to 20. Preferably, k may be from 2 to1000, 50 to 500 or 2 to 50.

In certain variations, R¹ or R² may be a C₄-C₅₀₀₀ branched alkyl grouprepresented by formula (F-II) above where n is larger than one (1), andat least 50% (e.g., at least 60%, 70%, 80%, 90%, or even 95%) of R⁶ arehydrogen, and at least 50% (e.g., at least 60%, 70%, 80%, 90%, or even95%) of R⁷ are independently C₁-C₃₀ linear alkyl groups. In certainvariations among these where a portion of R⁶ and at least a portion ofR⁷ are alkyl groups, at least 80% of those R⁶ that are alkyl groups areC₁-C₄ linear alkyl groups, and at least 80% of R⁷ are C₄-C₃₀ linearalkyl groups. In certain variations, all of R⁶ are hydrogen, and all ofR⁷ are independently C₁-C₃₀ linear alkyl groups. In certain variations,all of R⁶ are hydrogen, and all of R⁷ are identical C₁-C₃₀ linear alkylgroups.

In certain variations, R¹ or R² may be a C₄-C₅₀₀₀ branched alkyl grouprepresented by formula (F-II) above where n is larger than one (1), andat least 50% (e.g., at least 60%, 70%, 80%, 90%, or even 95%) of R⁷ arehydrogen, and at least 50% (e.g., at least 60%, 70%, 80%, 90%, or even95%) of R⁶ are independently C₁-C₃₀ linear alkyl groups. In certainvariations among these where a portion of R⁷ and at least a portion ofR⁶ are alkyl groups, at least 80% of those R⁷ that are alkyl groups areC₁-C₄ linear alkyl groups, and at least 80% of R⁶ are C₄-C₃₀ linearalkyl groups. In certain variations, all of R⁷ are hydrogen, and all ofR⁶ are independently C₁-C₃₀ linear alkyl groups. In certain variations,all of R⁷ are hydrogen, and all of R⁶ are identical C₁-C₃₀ linear alkylgroups.

Additionally or alternatively, R⁴ may be a C₁-C₅₀ alkyl group, a C₁-C₃₀₀alkyl group, a C₁-C₁₀₀ alkyl group, a C₁-C₅₀ alkyl group, a C₁-C₃₀ alkylgroup or a C₁-C₁₀ alkyl group. The alkyl group may be linear orbranched. In particular, R⁴ may be a C₁-C₅₀ alkyl group, moreparticularly, a C₁-C₅₀ linear alkyl group or a C₁-C₃₀ linear alkylgroup.

Additionally or alternatively, R⁴ may be an unsubstituted or substitutedphenyl group. For example, the phenyl group may be substituted with oneor more C₁-C₅₀ alkyl groups, preferably, one or more C₁-C₃₀ alkylgroups, or more preferably, one or more C₁-C₁₀ alkyl groups.

Additionally or alternatively, R⁵ may be hydrogen.

In one embodiment, n may be 1, R¹ and R² may independently be a C₁-C₁₀₀alkyl group or a C₁-C₃₀ alkyl group, R³ may be hydrogen or a C₁-C₁₀₀alkyl group, R⁴ may be a C₁-C₅₀ alkyl group, and R⁵ may be hydrogen.

Additionally or alternatively, R⁵ may be a C₁-C₃₀ alkyl group, a C₁-C₁₀alkyl group, a C₁-C₄ alkyl group or a C₁-C₂ alkyl group. The alkyl groupmay be linear or branched. It is understood herein that R⁵ may be bondedto the phenyl moiety at any suitable location with respect to the —O—R⁴moiety, namely the para (p-), meta (m-), or ortho (o-) position withrespect to the —O—R⁴ moiety.

Examples of compounds of formula (F-I) are shown below in TABLE II.

TABLE II Exemplary Compounds of Formula (F-I)

(1) 1-methoxy-4-(9-methylnonadecan-9-yl)benzene

(2) 1-methoxy-2-(9-methylnonadecan-9-yl)benzene

(3) 1-methoxy-3-(9-methylnonadecan-9-yl)benzene

The compounds of formula (F-I) described herein may have various levelsof regio-regularity. For example, each compound of formula (F-I) may besubstantially atactic, isotactic, or syndiotactic. The compounds,however, can be a mixture of different molecules, each of which can beatactic, isotactic, or syndiotactic. Without intending to be bound by aparticular theory, however, it is believed that regio-regular molecules,especially the isotactic ones, due to the regular distribution of thependant groups, especially the longer ones, tend to contribute toincreased performance (e.g., electrohydrodynamic lubricationperformance) of base stocks comprising those compounds of formula (F-I)described herein. Thus, it is preferred that at least about 50 mol %, orat least about 60 mol %, or at least about 70 mol %, or at least about75 mol %, or at least about 80 mol %, or at least about 90 mol %, oreven about 95 mol % of the compounds of formula (F-I) described hereinare regio-regular. It is further preferred that at least about 50 mol %,or at least about 60 mol %, or at least about 70 mol %, or at leastabout 75 mol %, or at least about 80 mol %, or at least about 90 mol %,or even about 95 mol %, of compounds of formula (F-I) described hereinare isotactic.

III. Processes for Making the Alkylated Anisole Compounds

Processes for making the compounds of formula (F-I) are provided herein.In particular, the process comprises reacting a compound having thefollowing formula (F-Ia):

with an olefin-containing material comprising a compound having thefollowing formula (F-Ib):

in the presence of an acid catalyst, wherein R¹, R², R³, R⁴ and m are asdescribed above in association with formula (F-I).

As described herein, alkylated anisoles of formula (F-I) can beselectively synthesized from a uPAO (formula (F-Ib)) and ananisole-derivative compound (formula (F-Ia)) in the presence of an acidcatalyst such that the anisole-derivative compound bonds to a tertiarycarbon of the uPAO. Thus, advantageously, the process described hereinhas a high selectivity for producing compounds that correspond instructure to formula (F-I). For example, at least about 50 mol %, atleast about 60 mol %, at least about 70 mol %, at least about 80 mol %,at least about 90 mol %, at least about 95 mol % or about 99 mol % ofthe compounds produced correspond in structure to formula (F-I).Additionally or alternatively, about 50 mol % to about 99 mol %, about70 mol % to about 99 mol %, about 80 mol % to about 99 mol %, or about90 mol % to about 99 mol % of the compounds produced correspond instructure to formula (F-I). Theoretically, even if this reaction has alower selectivity than 90 mol %, one can nonetheless purify the productmixture to obtain a final product having higher than 90 mol % of purityof the intended product. In some instances, the balance of the alkylatedanisoles formed have the anisole-derivative compound bonded to a primaryor secondary carbon of the uPAO.

Further, the process described herein has a high selectivity forproducing compounds corresponding in structure to formula (F-I) whereinthe moiety comprising R¹, R², and R³ may be bonded to the phenyl ring atposition para to the —O—R⁴ moiety. For example, at least about 70 mol %,at least about 80 mol %, at least about 90 mol %, at least about 95 mol% or about 99 mol % of the compounds produced correspond in structure toformula (F-I) where the moiety comprising R¹, R², and R³ is bonded tothe phenyl ring at position para to the —O—R⁴ moiety. Additionally oralternatively, about 70 mol % to about 99 mol %, about 80 mol % to about99 mol %, or about 90 mol % to about 99 mol % of the compounds producedcorrespond in structure to formula (F-I) where the moiety comprising R¹,R², and R³ is bonded to the phenyl ring at position para to the —O—R⁴moiety.

Additionally or alternatively, the process described herein may have ahigh selectivity for producing compounds corresponding in structure toformula (F-I), which are monoalkylated (i.e., where n is 1). Forexample, at least about 70 mol %, at least about 80 mol %, at leastabout 90 mol %, at least about 95 mol % or about 99 mol % of thecompounds produced correspond in structure to formula (F-I) n is 1.Additionally or alternatively, about 70 mol % to about 99 mol %, about80 mol % to about 99 mol %, or about 90 mol % to about 99 mol % of thecompounds produced correspond in structure to formula (F-I) where n is1.

In various aspects, R³ may be hydrogen. In some instances, theolefin-containing material may comprise one or more olefin compounds offormula (F-Ib), where R³ is hydrogen, in an amount of at least about 1.0wt %, at least about 10 wt %, at least about 20 wt %, at least about 30wt %, at least about 40 wt %, at least about 50 wt %, at least about 60wt %, at least about 70 wt %, at least about 75 wt %, at least about 80wt %, at least about 90 wt %, at least about 99 wt %, or about 100 wt %based on the total weight of the olefin-containing material. Inparticular, the olefin-containing material may comprise one or moreolefin compounds of formula (F-Ib), where R³ is hydrogen, in an amountof at least about 75 wt %. Additionally or alternatively, theolefin-containing material may comprise a compound of formula (F-Ib),where R³ is hydrogen, in an amount of about 1.0 wt % to about 100 wt %,1.0 wt % to about 90 wt %, about 20 wt % to about 90 wt %, about 40 wt %to about 90 wt %, about 50 wt % to about 90 wt %, about 60 wt % to about90 wt %, about 75 wt % to about 90 wt % or about 80 wt % to about 90 wt%.

Alternatively, R³ may be a C₁-C₅₀₀₀ alkyl group, a C₁-C₄₀₀₀ alkyl group,a C₁-C₃₀₀₀ alkyl group, a C₁-C₂₀₀₀ alkyl group, a C₁-C₁₀₀₀ alkyl group,a C₁-C₉₀₀ alkyl group, a C₁-C₈₀₀ alkyl group, a C₁-C₇₀₀ alkyl group, aC₁-C₆₀₀ alkyl group, a C₁-C₅₀₀ alkyl group, a C₁-C₄₀₀ alkyl group, aC₁-C₃₀₀ alkyl group, a C₁-C₂₀₀ alkyl group, a C₁-C₁₀₀ alkyl group, aC₁-C₅₀ alkyl group, a C₁-C₃₀ alkyl group, or C₁-C₁₀ alkyl group. Inparticular, R³ may be a C₁-C₁₀₀ alkyl group. In some instances, theolefin-containing material may comprise one or more compounds of formula(F-Ib), where R³ is an alkyl group (e.g., C₁-C₁₀₀ alkyl group), in anamount of at least about 1.0 wt %, at least about 10 wt %, at leastabout 20 wt %, at least about 25 wt %, at least about 30 wt %, at leastabout 40 wt %, at least about 50 wt %, at least about 60 wt %, at leastabout 70 wt %, at least about 75 wt %, at least about 80 wt %, at leastabout 90 wt %, at least about 99 wt %, or about 100 wt % based on thetotal weight of the olefin-containing material. In particular, theolefin-containing material may comprise a compound of formula (F-Ib),where R³ is an alkyl group (e.g., C₁-C₁₀₀ alkyl group) in an amount ofat least about 50 wt %. Additionally or alternatively, theolefin-containing material may comprise a compound of formula (F-Ib),where R³ is an alkyl group (e.g., C₁-C₁₀₀ alkyl group), in an amount ofabout 1.0 wt % to about 100 wt %, 1.0 wt % to about 90 wt %, about 10 wt% to about 60 wt %, about 10 wt % to about 50 wt %, about 10 wt % toabout 40 wt % or about 10 wt % to about 25 wt %.

In some embodiments, the olefin-containing material may comprise amixture of compounds of formula (F-Ib). For example, theolefin-containing material may comprise a mixture of: (i) one or moreolefin compounds of formula (F-Ib) wherein R³ is hydrogen; and (ii) oneor more olefin compounds of formula (F-Ib) wherein R³ is an alkyl group(e.g., C₁-C₁₀₀ alkyl group). In some embodiments, the olefin-containingmaterial may comprise a mixture of: (i) about 1.0 wt % to about 99 wt %of one or more olefin compounds of formula (F-Ib) wherein R³ ishydrogen; and (ii) about 1.0 wt % to about 99 wt % of one or more olefincompounds of formula (F-Ib) wherein R³ is an alkyl group (e.g., C₁-C₁₀₀alkyl group). In particular, the olefin-containing material may comprisea mixture of: (i) about 50 wt % to about 90 wt % or about 75 wt % toabout 90 wt % of one or more olefin compounds of formula (F-Ib) whereinR³ is hydrogen; and (ii) about 10 wt % to about 50 wt % or about 10 wt %to about 25 wt % of one or more olefin compounds of formula (F-Ib)wherein R³ is an alkyl group (e.g., C₁-C₁₀₀ alkyl group).

The olefin-containing materials used in the process may be PAO (mPAO,cPAO, and mixtures thereof) dimers (C₄-C₁₀₀), trimers (C₆-C₁₀₀),tetramers (C₁-C₁₀₀) and higher oligomers, pentamer, hexamer, and thelike, or alpha-olefins (e.g., C₂-C₃₀ alpha-olefin). Suitablealpha-olefins include, for example, alkyl olefins such as 1-hexene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, and thelike.

The PAO dimer (e.g., mPAO, cPAO) can be any dimer with terminal C═Cdouble bond prepared by using metallocene or other single-site catalyst.The dimer can be from an alpha-olefin (e.g., C₂-C₃₀ alpha-olefin), forexample, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-octadecene or a combination of alpha-olefins. In particular, theolefin-containing material in the process provided herein may beproduced by oligomerization of a C₁-C₁₀₀ alpha-olefin in the presence ofa metallocene compound. Metallocene-catalyzed alpha-olefinoligomerization processes are described in U.S. Pat. Nos. 5,688,887 and6,043,401 and WO 2007/011973, each of which is incorporated herein byreference in its entirety and to which reference is made for details offeeds, metallocene catalysts, process conditions and characterizationsof products.

In some examples, at least about 50 mol %, or at least about 60 mol %,or at least about 70 mol %, or at least about 75 mol %, or at leastabout 80 mol %, or at least about 90 mol %, or even about 95 mol %, ofthe olefin-containing materials described herein are isotactic. Inparticular, at least about 60 mol %, or at least about 75 mol %, or atleast about 80 mol % of the olefin-containing materials described hereinare isotactic.

The cPAOs may be made by using conventional catalysts to formolefin-containing material having a formula (F-Ib). Examples of suitableconventional catalysts include but are not limited to Lewis acidcompounds, such as BF3, AlCl3, aluminum trialkyls, or combinationsthereof. When using conventional catalysts, the resultantolefin-containing material tends to be a mixture of olefin compoundswith highly varied R¹, R², and R³. At least one of R¹, R² and R³ may bean alkyl group having a carbon backbone chain having multiple pendantgroups attached thereto, many of which are short-chain alkyl groups suchas methyl, ethyl, and the like. The distribution of such pendant groupson the backbone chain can be random. Such unhydrogenated cPAOs obtainedby using conventional catalysts typically may be atactic. Processes forthe production of cPAOs are disclosed, for example, in the followingpatents, each of which is incorporated herein by reference in itsentirety: U.S. Pat. Nos. 3,149,178; 3,382,291; 3,742,082; 3,769,363;3,780,128; 4,172,855; and 4,956,122; as well as in Shubkin, R. L. (Ed.)(1992) Synthetic Lubricants and High-Performance Functional Fluids(Chemical Industries) New York: Marcel Dekker Inc.

PAO lubricant compositions in which little double bond isomerization isfound has resulted in different classes of high viscosity index PAO(HVI-PAO), which are also contemplated for use herein. In one class ofHVI-PAO, a reduced chromium catalyst is reacted with an alpha-olefinmonomer. Such PAOs are described in U.S. Pat. Nos. 4,827,073; 4,827,064;4,967,032; 4,926,004; and 4,914,254, each of which is incorporatedherein by reference in its entirety.

As described herein, R⁴ may be an alkyl group (e.g., a C₁-C₅₀ alkylgroup, a C₁-C₄₀ alkyl group, a C₁-C₃₀ alkyl group, a C₁-C₂₀ alkyl group,a C₁-C₁₀ alkyl group, a C₁-C₈ alkyl group, etc.). Further, R⁵ may behydrogen or an alkyl group as described herein (e.g., a C₁-C₅₀ alkylgroup, a C₁-C₄₀ alkyl group, a C₁-C₃₀ alkyl group, a C₁-C₂₀ alkyl group,a C₁-C₁₀ alkyl group, a C₁-C₈ alkyl group, a C₁-C₄ alkyl group, a C₁-C₂alkyl group).

Suitable acid catalysts that can be used in the processes describedherein for making the compound having formula (F-I) include, forexample, a Lewis acid. The Lewis acid catalysts useful for couplingreactions include metal and metalloid halides conventionally used asFriedel-Crafts catalysts. Suitable examples include AlCl₃, BF₃, AlBr₃,TiCl₃, and TiCl₄, either as such or with a protic promoter. Otherexamples include solid Lewis acid catalysts; acid clays; polymericacidic resins; amorphous solid catalysts, such as silica-alumina; andheteropoly acids, such as the tungsten zirconates, tungsten molybdates,tungsten vanadates, phosphotungstates and molybdotungstovanadogermanates(e.g. WO_(x)/ZrO₂ and WO_(x)/MoO₃). Beside these catalysts, acidic ionicliquid can also be used as catalysts for coupling reactions. Amongdifferent catalysts polymeric acidic resins, such as Amberlyst 15 andAmberlyst 36 are most preferred. In particular, the acid catalyst may bea solid acid catalyst selected from the group consisting of a solidLewis acid, an acid clay, a polymeric acidic resin, silica-alumina, amineral acid and a combination thereof. Examples of suitable mineralacids include, but are not limited to hydrochloric acid (HCl),hydrobromic acid (HBr), hydrofluoric acid (HF), sulfuric acid (H₂SO₄),phosphoric acid (H₃PO₄), nitric acid (HNO₃) and combinations thereof.

Other suitable acid catalysts include molecular sieve materials, such assynthetic or natural zeolites. For example, the acid catalyst maycomprise a molecular sieve having a framework structure selected fromthe group consisting of BEA, EUO, FAU, FER, HEU, MEL, MFI, MOR, MRE,MTW, MTT, MWW, OFF, and combinations thereof. Examples of molecularsieve materials having such a framework structure include, but are notlimited to ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-48, ZSM-50,Zeolite Beta, MCM-56, MCM-22, MCM-36, MCM-49, zeolite Y, zeolite X, andcombinations thereof. In particular, the acid catalyst may compriseMCM-49 or zeolite Y.

A person of ordinary skill in the art knows how to make theaforementioned frameworks and molecular sieves. For example, see thereferences provided in the International Zeolite Association's databaseof zeolite structures found at www.iza-structure.org/databases.

Typically, the amount of acid catalyst used is 0.1 to 30 weight % andpreferably 0.2 to 5 weight % based on total weight of the feed.

Reaction conditions for the process described herein, such astemperature, pressure and contact time, may also vary greatly and anysuitable combination of such conditions may be employed herein. Thereaction temperature may range between about 25° C. to about 250° C.,and preferably between about 30° C. to about 200° C., and morepreferably between about 60° C. to about 175° C. The reaction may becarried out under ambient pressure and the contact time may vary from amatter of seconds or minutes to a few hours or greater. The reactantscan be added to the reaction mixture or combined in any order. The stirtime employed can range from 0.5 to 48 hours, preferably from 1 to 36hours, and more preferably from 2 to 24 hours.

IV. Lubricant Oil and Base Stock Compositions

This disclosure provides lubricating oils useful as engine oils and inother applications characterized by excellent stability, solvency anddispersancy characteristics. The lubricating oils are based on highquality base stocks including a major portion comprising one or morecompounds corresponding in structure to formula (F-1) as describedherein. Alternatively, base stocks including a major portion of othercomponents, such as a Group I, II and/or III mineral oil base stocks,GTL, Group IV (e.g., PAO), Group V (e.g., esters, alkylated aromatics,PAG) and combinations thereof, and a minor portion comprising one ormore compounds corresponding in structure to formula (F-1) as describedherein as a co-base stock are also provided herein. The lubricating oilbase stock can be any oil boiling in the lube oil boiling range,typically between about 100 to about 450° C. In the presentspecification and claims, the terms base oil(s) and base stock(s) areused interchangeably.

The viscosity-temperature relationship of a lubricating oil is one ofthe critical criteria which must be considered when selecting alubricant for a particular application. Viscosity Index (VI) is anempirical, unitless number which indicates the rate of change in theviscosity of an oil within a given temperature range. Fluids exhibitinga relatively large change in viscosity with temperature are said to havea low viscosity index. A low VI oil, for example, will thin out atelevated temperatures faster than a high VI oil. Usually, the high VIoil is more desirable because it has higher viscosity at highertemperature, which translates into better or thicker lubrication filmand better protection of the contacting machine elements.

In another aspect, as the oil operating temperature decreases, theviscosity of a high VI oil will not increase as much as the viscosity ofa low VI oil. This is advantageous because the excessive high viscosityof the low VI oil will decrease the efficiency of the operating machine.Thus high VI (HVI) oil has performance advantages in both high and lowtemperature operation. VI is determined according to ASTM method D2270-93 [1998]. VI is related to kinematic viscosities measured at 40°C. and 100° C. using ASTM Method D 445-01.

IV.A. Lubricating Oil Base Stocks

A wide range of lubricating oils is known in the art. Lubricating oilsthat are useful in the present disclosure are both natural oils andsynthetic oils. Natural and synthetic oils (or mixtures thereof) can beused unrefined, refined, or re-refined (the latter is also known asreclaimed or reprocessed oil). Unrefined oils are those obtaineddirectly from a natural or synthetic source and used without addedpurification. These include shale oil obtained directly from retortingoperations, petroleum oil obtained directly from primary distillation,and ester oil obtained directly from an esterification process. Refinedoils are similar to the oils discussed for unrefined oils except refinedoils are subjected to one or more purification steps to improve the atleast one lubricating oil property. One skilled in the art is familiarwith many purification processes. These processes include solventextraction, secondary distillation, acid extraction, base extraction,filtration, and percolation. Re-refined oils are obtained by processesanalogous to refined oils but using an oil that has been previously usedas a feed stock.

Groups I,II, III, IV and V are broad categories of base oil stocksdeveloped and defined by the American Petroleum Institute (APIPublication 1509; www.API.org) to create guidelines for lubricant baseoils. Group I base stocks generally have a viscosity index of from 80 to120 and contain greater than 0.03% sulfur and less than 90% saturates.Group II base stocks generally have a viscosity index of from 80 to 120,and contain less than or equal to 0.03% sulfur and greater than or equalto 90% saturates. Group III stock generally has a viscosity indexgreater than 120 and contains less than or equal to 0.03% sulfur andgreater than 90% saturates. Group IV includes polyalpha-olefins (PAO).Group V base stocks include base stocks not included in Groups I-IV.TABLE III below summarizes properties of each of these five groups.

TABLE III Base Oil Properties Saturates Sulfur Viscosity Index Group I<90 and/or >0.03% and ≥80 and <120 Group II ≥90 and ≤0.03% and ≥80 and<120 Group III ≥90 and ≤0.03% and ≥120 Group IV Includes PAO productsGroup V All other base oil stocks not included in Groups I, II, III orIV

Natural oils include animal oils, vegetable oils (castor oil and lardoil, for example), and mineral oils. Animal and vegetable oilspossessing favorable thermal oxidative stability can be used. Of thenatural oils, mineral oils are preferred. Mineral oils vary widely as totheir crude source, for example, as to whether they are paraffinic,naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal orshale are also useful in the present disclosure. Natural oils vary alsoas to the method used for their production and purification, forexample, their distillation range and whether they are straight run orcracked, hydrorefined, or solvent extracted.

Group II and/or Group III hydroprocessed or hydrocracked base stocks, aswell as synthetic oils such as polyalpha-olefins, alkyl aromatics andsynthetic esters, i.e. Group IV and Group V oils are also well knownbase stock oils.

Synthetic oils include hydrocarbon oil such as polymerized andinterpolymerized olefins (polybutyl ones, polypropylenes, propyleneisobutylene copolymers, ethylene-olefin copolymers, andethylene-alpha-olefin copolymers, for example). PAO oil base stocks, theGroup IV API base stocks, are a commonly used synthetic hydrocarbon oil.By way of example, PAOs derived from C₈, C₁₀, C₁₂, C₁₄ olefins ormixtures thereof may be utilized. See U.S. Pat. Nos. 4,956,122;4,827,064; and 4,827,073, which are incorporated herein by reference intheir entirety. Group IV oils, that is, the PAO base stocks haveviscosity indices preferably greater than 130, more preferably greaterthan 135, still more preferably greater than 140.

In one particular embodiment, a lubricant base stock is provided. Thelubricant base stock may comprise one or more of the compounds offormula (F-I) as described herein. Also contemplated herein, areformulated lubricant oil compositions comprising one or more of thelubricant base stocks described herein.

As discussed herein, the compounds of formula (F-I) unexpectedly have acombination of desirable properties. For example, compositionscomprising compounds of formula (F-I), e.g., lubricant base stockcompositions provided herein, may have a rotating pressure vesseloxidation test (RPVOT) break time, measured according to ASTM standardD-2272, of at least about 200 minutes, at least about 300 minutes, atleast about 400 minutes, at least about 500 minutes, at least about 600minutes, at least about 700 minutes, at least about 800 minutes, atleast about 850 minutes, at least about 900 minutes or about 1000minutes. Additionally or alternatively, compositions comprisingcompounds of formula (F-I), e.g., lubricant base stock compositionsprovided herein, may have an RPVOT break time of about 200 to about 1000minutes, about 200 to about 900 minutes, about 300 to about 900 minutes,or about 300 to about 800 minutes.

Further, compositions comprising compounds of formula (F-I), e.g.,lubricant base stock compositions provided herein, may have a kinematicviscosity at 100° C. (KV100), measured according to ASTM standard D-445,from about 1 to about 20 cSt, from about 1 to about 15 cSt, preferablyfrom about 2 to about 10 cSt, preferably from about 2 to about 5.5 cSt,or more preferably from about 5 to about 5.5 cSt.

Additionally or alternatively, compositions comprising compounds offormula (F-I), e.g., lubricant base stock compositions provided herein,may have a kinematic viscosity at 40° C. (KV40), measured according toASTM standard D-445, from about 10 to about 100 cSt, from about 10 toabout 50 cSt, preferably from about 20 to about 40 cSt, and morepreferably from about 20 to about 30 cSt.

Additionally or alternatively, compositions comprising compounds offormula (F-I), e.g., lubricant base stock compositions provided herein,may have a viscosity index (VI), measured according to ASTM standardD-2270, from about 25 to about 200, preferably from about 50 to about200, and more preferably from about 70 to about 200.

Additionally or alternatively, compositions comprising compounds offormula (F-I), e.g., lubricant base stock compositions provided herein,may have a Noack volatility of no greater than about 25%, preferably nogreater than about 20%, and more preferably no greater than about 18%.As used herein, Noack volatility is determined by ASTM D-5800.

Additionally or alternatively, compositions comprising compounds offormula (F-I), e.g., lubricant base stock compositions provided herein,may have a pour point), measured according to ASTM standard D-5950, ofabout 0.0° C., less than about −10° C., less than about −20° C., lessthan about −30° C., less than about −40° C., less than about −45° C.,less than about −50° C., less than about −55° C., less than about −60°C. or −70° C. Preferably, the compositions provided herein may have apour point of less than about −55° C. The compositions provided hereinmay have a pour point of about −70° C. to about 0.0° C., about −70° C.to about −10° C., about −70° C. to about −20° C., about −70° C. to about−30° C., about −70° C. to about −40° C., about −70° C. to about −45° C.,or about −70° C. to about −50° C.

Additionally or alternatively, compositions comprising compounds offormula (F-I), e.g., lubricant base stock compositions provided herein,may have a Brookfield viscosity at −40° C., measured according to ASTMstandard D-2983, from about 10000 to about 30000 cP, preferably fromabout 15000 to about 25000 cP, and more preferably from about 17,500 toabout 22,500 cP.

Additionally or alternatively, compositions comprising compounds offormula (F-I), e.g., lubricant base stock compositions provided herein,may have one or more of the following:

-   -   (i) a hydrolytic stability, measured according to ASTM D-2619,        of about 0.1 to about 1.0 mg KOH/g or about 0.1 to about 0.5 mg        KOH/g;    -   (ii) a low foaming tendency, measured according to ASTM D-892,        at least lower than alkylated naphthalene base stocks; and    -   (iii) a solubility, measured according to Fedors Correlation, of        about 8 to about 10 d(i) at 25° C. (cal/cc){circumflex over        ( )}1/2.        Compositions comprising compounds of formula (F-I), e.g.,        lubricant base stock compositions provided herein, may have two        of (i)-(iii) (e.g., (i) and (ii), (i) and (iii), (ii) and (iii))        or all three of (i)-(iii).

Esters in a minor amount may be useful in the lubricating oils of thisdisclosure. Additive solvency and seal compatibility characteristics maybe secured by the use of esters such as the esters of dibasic acids withmonoalkanols and the polyol esters of monocarboxylic acids. Esters ofthe former type include, for example, the esters of dicarboxylic acidssuch as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipicacid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenylmalonic acid, etc., with a variety of alcohols such as butyl alcohol,hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc. Specificexamples of these types of esters include dibutyl adipate,di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate,diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecylphthalate, dieicosyl sebacate, etc.

Particularly useful synthetic esters are those which are obtained byreacting one or more polyhydric alcohols, preferably the hinderedpolyols such as the neopentyl polyols; e.g., neopentyl glycol,trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol, trimethylolpropane, pentaerythritol and dipentaerythritol with alkanoic acidscontaining at least 4 carbon atoms, preferably C₅ to C₃₀ acids such assaturated straight chain fatty acids including caprylic acid, capricacids, lauric acid, myristic acid, palmitic acid, stearic acid, arachicacid, and behenic acid, or the corresponding branched chain fatty acidsor unsaturated fatty acids such as oleic acid, or mixtures of any ofthese materials.

Esters should be used in an amount such that the improved wear andcorrosion resistance provided by the lubricating oils of this disclosureare not adversely affected.

Non-conventional or unconventional base stocks and/or base oils includeone or a mixture of base stock(s) and/or base oil(s) derived from: (1)one or more Gas-to-Liquids (GTL) materials, as well as (2) hydrodewaxed,or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/orbase oils derived from synthetic wax, natural wax or waxy feeds, mineraland/or non-mineral oil waxy feed stocks such as gas oils, slack waxes(derived from the solvent dewaxing of natural oils, mineral oils orsynthetic oils; e.g., Fischer-Tropsch feed stocks), natural waxes, andwaxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxyraffinate, hydrocrackate, thermal crackates, foots oil or other mineral,mineral oil, or even non-petroleum oil derived waxy materials such aswaxy materials recovered from coal liquefaction or shale oil, linear orbranched hydrocarbyl compounds with carbon number of 20 or greater,preferably 30 or greater and mixtures of such base stocks and/or baseoils.

GTL materials are materials that are derived via one or more synthesis,combination, transformation, rearrangement, and/ordegradation/deconstructive processes from gaseous carbon-containingcompounds, hydrogen-containing compounds and/or elements as feed stockssuch as hydrogen, carbon dioxide, carbon monoxide, water, methane,ethane, ethylene, acetylene, propane, propylene, propyne, butane,butylenes, and butynes. GTL base stocks and/or base oils are GTLmaterials of lubricating viscosity that are generally derived fromhydrocarbons; for example, waxy synthesized hydrocarbons, that arethemselves derived from simpler gaseous carbon-containing compounds,hydrogen-containing compounds and/or elements as feed stocks. GTL basestock(s) and/or base oil(s) include oils boiling in the lube oil boilingrange (1) separated/fractionated from synthesized GTL materials such as,for example, by distillation and subsequently subjected to a final waxprocessing step which involves either or both of a catalytic dewaxingprocess, or a solvent dewaxing process, to produce tube oils ofreduced/low pour point; (2) synthesized wax isomerates, comprising, forexample, hydrodewaxed or hydroisomerized cat and/or solvent dewaxedsynthesized wax or waxy hydrocarbons; (3) hydrodewaxed orhydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T)material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possibleanalogous oxygenates); preferably hydrodewaxed orhydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxyhydrocarbons, or hydrodewaxed or hydroisomerized/followed by cat (orsolvent) dewaxing dewaxed, F-T waxes, or mixtures thereof.

GTL base stock(s) and/or base oil(s) derived from GTL materials,especially, hydrodewaxed or hydroisomerized/followed by cat and/orsolvent dewaxed wax or waxy feed, preferably F-T material derived basestock(s) and/or base oil(s), are characterized typically as havingkinematic viscosities at 100° C. of from 2 mm²/s to 50 mm²/s (ASTMD445). They are further characterized typically as having pour points of−5° C. to −40° C. or lower (ASTM D97). They are also characterizedtypically as having viscosity indices of 80 to 140 or greater (ASTMD2270).

In addition, the GTL base stock(s) and/or base oils) are typicallyhighly paraffinic (>90% saturates), and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s)typically have very low sulfur and nitrogen content, generallycontaining less than 10 ppm, and more typically less than 5 ppm of eachof these elements. The sulfur and nitrogen content of GTL base stock(s)and/or base oil(s) obtained from F-T material, especially F-T wax, isessentially nil. In addition, the absence of phosphorous and aromaticsmake this materially especially suitable for the formulation of low SAPproducts.

The term GTL base stock and/or base oil and/or wax isomerate base stockand/or base oil is to be understood as embracing individual fractions ofsuch materials of wide viscosity range as recovered in the productionprocess, mixtures of two or more of such fractions, as well as mixturesof one or two or more low viscosity fractions with one, two or morehigher viscosity fractions to produce a blend wherein the blend exhibitsa target kinematic viscosity.

The GTL material, from which the GTL base stock(s) and/or base oil(s)is/are derived is preferably an F-T material (i.e., hydrocarbons, waxyhydrocarbons, wax).

Base oils for use in the formulated lubricating oils useful in thepresent disclosure are any of the variety of oils corresponding to APIGroup I, Group II, Group III, Group IV, Group V and Group VI oils andmixtures thereof, preferably API Group II, Group III, Group IV, Group Vand Group VI oils and mixtures thereof, more preferably the Group III toGroup VI base oils due to their exceptional volatility, stability,viscometric and cleanliness features. Minor quantities of Group I stock,such as the amount used to dilute additives for blending into formulatedlube oil products, can be tolerated but should be kept to a minimum,i.e. amounts only associated with their use as diluent/carrier oil foradditives used on an “as received” basis. Even in regard to the Group IIstocks, it is preferred that the Group II stock be in the higher qualityrange associated with that stock, i.e. a Group II stock having aviscosity index in the range 100<VI<120.

In addition, the GTL base stock(s) and/or base oil(s) are typicallyhighly paraffinic (>90% saturates), and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s) andhydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed basestock(s) and/or base oil(s) typically have very low sulfur and nitrogencontent, generally containing less than 10 ppm, and more typically lessthan 5 ppm of each of these elements. The sulfur and nitrogen content ofGTL, base stock(s) and/or base oil(s) obtained from F-T material,especially F-T wax, is essentially nil. In addition, the absence ofphosphorous and aromatics make this material especially suitable for theformulation of low sulfur, sulfated ash, and phosphorus (low SAP)products.

The lubricating oils are based on high quality base stocks including amajor portion comprising one or more compounds corresponding instructure to formula (F-1) as described herein. Alternatively, basestocks including a major portion of other components, such as a Group I,II and/or III mineral oil base stocks, GTL, Group IV (e.g., PAO), GroupV (e.g., esters, alkylated aromatics, PAG), and minor portion comprisingone or more compounds corresponding in structure to formula (F-1) asdescribed herein as a co-base stock are also provided herein.

As stated above, lubricant base stocks comprising one or more compoundscorresponding in structure to formula (F-1) as described herein may bepresent in lubricating oil compositions as a primary component lubricantbase stock or a minor lubricant co-base stock component. Thus, theformulated lubricant compositions disclosed herein may comprise thelubricant base stock in an amount from about 1 wt % to about 99 wt % orabout 5 wt % to about 90 wt %. For example, when present as a primarycomponent, the lubricant base stock described herein may be present inlubricating oils from about 50 wt % to about 99 wt % of the totalcomposition (all proportions and percentages set out in thisspecification are by weight unless the contrary is stated) and moreusually in the range of about 80 wt % to about 99 wt % or about 80 wt %to about 90 wt %. Alternatively, when present as a minor co-base stockcomponent, the lubricant base stock described herein may be present inlubricating oils from about 1 wt % to about 50 wt % of the totalcomposition (all proportions and percentages set out in thisspecification are by weight unless the contrary is stated), preferablyfrom about 5 wt % to about 30 wt % and more preferably from about 10 wt% to about 20 wt %.

IV.B. Additives

The formulated lubricating oil useful in the present disclosure mayadditionally contain one or more of the other commonly used lubricatingoil performance additives including but not limited to dispersants,other detergents, corrosion inhibitors, rust inhibitors, metaldeactivators, other anti-wear agents and/or extreme pressure additives,anti-seizure agents, wax modifiers, viscosity index improvers, viscositymodifiers, fluid-loss additives, seal compatibility agents, otherfriction modifiers, lubricity agents, anti-staining agents, chromophoricagents, defoamants, demulsifiers, emulsifiers, densifiers, wettingagents, gelling agents, tackiness agents, colorants, and others. For areview of many commonly used additives, see Klamann in Lubricants andRelated Products, Verlag Chemie, Deerfield Beach, Fla.; ISBN0-89573-177-0. Reference is also made to “Lubricant Additives Chemistryand Applications” edited by Leslie R. Rudnick, Marcel Dekker, Inc. NewYork, 2003 ISBN: 0-8247-0857-1.

The types and quantities of performance additives used in combinationwith the instant disclosure in lubricant compositions are not limited bythe examples shown herein as illustrations.

IV.C. Viscosity Improvers

Viscosity improvers (also known as Viscosity Index modifiers, and VIimprovers) increase the viscosity of the oil composition at elevatedtemperatures which increases film thickness, while having limited effecton viscosity at low temperatures.

Suitable viscosity improvers include high molecular weight hydrocarbons,polyesters and viscosity index improver dispersants that function asboth a viscosity index improver and a dispersant. Typical molecularweights of these polymers are from 10,000 to 1,000,000, more typically20,000 to 500,000, and even more typically between 50,000 and 200,000.

Examples of suitable viscosity improvers are polymers and copolymers ofmethacrylate, butadiene, olefins, or alkylated styrenes. Polyisobutyleneis a commonly used viscosity index improver. Another suitable viscosityindex improver is polymethacrylate (copolymers of various chain lengthalkyl methacrylates, for example), some formulations of which also serveas pour point depressants. Other suitable viscosity index improversinclude copolymers of ethylene and propylene, hydrogenated blockcopolymers of styrene and isoprene, and polyacrylates (copolymers ofvarious chain length acrylates, for example). Specific examples includestyrene-isoprene or styrene-butadiene based polymers of 50,000 to200,000 molecular weight.

The amount of viscosity modifier may range from zero to 8 wt %,preferably zero to 4 wt %, more preferably zero to 2 wt % based onactive ingredient and depending on the specific viscosity modifier used.

IV.D. Antioxidants

Typical antioxidant include phenolic antioxidants, aminic antioxidantsand oil-soluble copper complexes. Detailed description of suchantioxidants and their quantities of use can be found, e.g., in WO2015/060984 A1, the relevant portions thereof are incorporated herein byreferene in their entirety.

IV.E. Detergents

In addition to the alkali or alkaline earth metal salicylate detergentwhich is an essential component in the present disclosure, otherdetergents may also be present. While such other detergents can bepresent, it is preferred that the amount employed be such as to notinterfere with the synergistic effect attributable to the presence ofthe salicylate. Therefore, most preferably such other detergents are notemployed.

If such additional detergents are present, they can include alkali andalkaline earth metal phenates, sulfonates, carboxylates, phosphonatesand mixtures thereof. These supplemental detergents can have total basenumber (TBN) ranging from neutral to highly overbased, i.e. TBN of 0 toover 500, preferably 2 to 400, more preferably 5 to 300, and they can bepresent either individually or in combination with each other in anamount in the range of from 0 to 10 wt %, preferably 0.5 to 5 wt %(active ingredient) based on the total weight of the formulatedlubricating oil. As previously stated, however, it is preferred thatsuch other detergent not be present in the formulation.

Such additional other detergents include by way of example and notlimitation calcium phenates, calcium sulfonates, magnesium phenates,magnesium sulfonates and other related components (including borateddetergents).

IV.F. Dispersants

During engine operation, oil-insoluble oxidation byproducts areproduced. Dispersants help keep these byproducts in solution, thusdiminishing their deposition on metal surfaces. Dispersants may beashless or ash-forming in nature. Preferably, the dispersant is ashless.So called ashless dispersants are organic materials that formsubstantially no ash upon combustion. For example, non-metal-containingor borated metal-free dispersants are considered ashless. In contrast,metal-containing detergents discussed above form ash upon combustion.

Suitable dispersants typically contain a polar group attached to arelatively high molecular weight hydrocarbon chain. The polar grouptypically contains at least one element of nitrogen, oxygen, orphosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.

A particularly useful class of dispersants are the alkenylsuccinicderivatives, typically produced by the reaction of a long chainsubstituted alkenyl succinic compound, usually a substituted succinicanhydride, with a polyhydroxy or polyamino compound. The long chaingroup constituting the oleophilic portion of the molecule which conferssolubility in the oil, is normally a polyisobutylene group. Manyexamples of this type of dispersant are well known commercially and inthe literature. Exemplary patents describing such dispersants are U.S.Pat. Nos. 3,172,892; 3,219,666; 3,316,177 and 4,234,435. Other types ofdispersants are described in U.S. Pat. Nos. 3,036,003; and 5,705,458.

Hydrocarbyl-substituted succinic acid compounds are popular dispersants.In particular, succinimide, succinate esters, or succinate ester amidesprepared by the reaction of a hydrocarbon-substituted succinic acidcompound preferably having at least 50 carbon atoms in the hydrocarbonsubstituent, with at least one equivalent of an alkylene amine areparticularly useful.

Succinimides are formed by the condensation reaction between alkenylsuccinic anhydrides and amines. Molar ratios can vary depending on theamine or polyamine. For example, the molar ratio of alkenyl succinicanhydride to TEPA can vary from 1:1 to 5:1.

Succinate esters are formed by the condensation reaction between alkenylsuccinic anhydrides and alcohols or polyols. Molar ratios can varydepending on the alcohol or polyol used. For example, the condensationproduct of an alkenyl succinic anhydride and pentaerythritol is a usefuldispersant.

Succinate ester amides are formed by condensation reaction betweenalkenyl succinic anhydrides and alkanol amines. For example, suitablealkanol amines include ethoxylated polyalkylpolyamines, propoxylatedpolyalkylpolyamines and polyalkenylpolyamines such as polyethylenepolyamines. One example is propoxylated hexamethylenediamine.

The molecular weight of the alkenyl succinic anhydrides will typicallyrange between 800 and 2,500. The above products can be post-reacted withvarious reagents such as sulfur, oxygen, formaldehyde, carboxylic acidssuch as oleic acid, and boron compounds such as borate esters or highlyborated dispersants. The dispersants can be borated with from 0.1 to 5moles of boron per mole of dispersant reaction product.

Mannich base dispersants are made from the reaction of alkylphenols,formaldehyde, and amines. Process aids and catalysts, such as oleic acidand sulfonic acids, can also be part of the reaction mixture. Molecularweights of the alkylphenols range from 800 to 2,500.

Typical high molecular weight aliphatic acid modified Mannichcondensation products can be prepared from high molecular weightalkyl-substituted hydroxyaromatics or HN(R)₂ group-containing reactants.

Examples of high molecular weight alkyl-substituted hydroxyaromaticcompounds are polypropylphenol, polybutylphenol, and otherpolyalkylphenols. These polyalkylphenols can be obtained by thealkylation, in the presence of an alkylating catalyst, such as BF₃, ofphenol with high molecular weight polypropylene, polybutylene, and otherpolyalkylene compounds to give alkyl substituents on the benzene ring ofphenol having an average 600-100,000 molecular weight.

Examples of HN(R)₂ group-containing reactants are alkylene polyamines,principally polyethylene polyamines. Other representative organiccompounds containing at least one HN(R)₂ group suitable for use in thepreparation of Mannich condensation products are well known and includethe mono- and di-amino alkanes and their substituted analogs, e.g.,ethylamine and diethanol amine; aromatic diamines, e.g., phenylenediamine, diamino naphthalenes; heterocyclic amines, e.g., morpholine,pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamineand their substituted analogs.

Examples of alkylene polyamine reactants include ethylenediamine,diethylene triamine, triethylene tetraamine, tetraethylene pentaamine,pentaethylene hexamine, hexaethylene heptaamine, heptaethyleneoctaamine, octaethylene nonaamine, nonaethylene decamine, anddecaethylene undecamine and mixture of such amines having nitrogencontents corresponding to the alkylene polyamines, in the formulaH₂N—(Z—NH—)_(n)H, mentioned before, Z is a divalent ethylene and n is 1to 10 of the foregoing formula. Corresponding propylene polyamines suchas propylene diamine and di-, tri-, tetra-, pentapropylene tri-, tetra-,penta- and hexaamines are also suitable reactants. The alkylenepolyamines are usually obtained by the reaction of ammonia and dihaloalkanes, such as dichloro alkanes. Thus the alkylene polyamines obtainedfrom the reaction of 2 to 11 moles of ammonia with 1 to 10 moles ofdichloroalkanes having 2 to 6 carbon atoms and the chlorines ondifferent carbons are suitable alkylene polyamine reactants.

Aldehyde reactants useful in the preparation of the high molecularproducts useful in this disclosure include the aliphatic aldehydes suchas formaldehyde (also as paraformaldehyde and formalin), acetaldehydeand aldol (β-hydroxybutyraldehyde). Formaldehyde or aformaldehyde-yielding reactant is preferred.

Preferred dispersants include borated and non-borated succinimides,including those derivatives from mono-succinimides, leis-succinimides,and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbylsuccinimide is derived from a hydrocarbylene group such aspolyisobutylene having a Mn of from 500 to 5000 or a mixture of suchhydrocarbylene groups. Other preferred dispersants include succinicacid-esters and amides, alkylphenol-polyamine-coupled Mannich adducts,their capped derivatives, and other related components. Such additivesmay be used in an amount of 0.1 to 20 wt %, preferably 0.1 to 8 wt %,more preferably 1 to 6 wt % (on an as-received basis) based on theweight of the total lubricant.

IV.G. Pour Point Depressants

Conventional pour point depressants (also known as lube oil flowimprovers) may also be present. Pour point depressant may be added tolower the minimum temperature at which the fluid will flow or can bepoured. Examples of suitable pour point depressants include alkylatednaphthalenes polymethacrylates, polyacrylates, polyarylamides,condensation products of haloparaffin waxes and aromatic compounds,vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinylesters of fatty acids and allyl vinyl ethers. Such additives may be usedin amount of 0.0 to 0.5 wt %, preferably 0 to 0.3 wt %, more preferably0.001 to 0.1 wt % on an as-received basis.

IV.H. Corrosion Inhibitors/Metal Deactivators

Corrosion inhibitors are used to reduce the degradation of metallicparts that are in contact with the lubricating oil composition. Suitablecorrosion inhibitors include aryl thiazines, alkyl substituteddimercapto thiodiazoles thiadiazoles and mixtures thereof. Suchadditives may be used in an amount of 0.01 to 0.5 wt %, preferably 0.01to 1.5 wt %, more preferably 0.01 to 0.2 wt %, still more preferably0.01 to 0.1 wt % (on an as-received basis) based on the total weight ofthe lubricating oil composition.

IV.I. Seal Compatibility Additives

Seal compatibility agents help to swell elastomeric seals by causing achemical reaction in the fluid or physical change in the elastomer.Suitable seal compatibility agents for lubricating oils include organicphosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzylphthalate, for example), and polybutenyl succinic anhydride andsulfolane-type seal swell agents such as Lubrizol 730-type seal swelladditives. Such additives may be used in an amount of 0.01 to 3 wt %,preferably 0.01 to 2 wt % on an as-received basis.

IV.J. Anti-Foam Agents

Anti-foam agents may advantageously be added to lubricant compositions.These agents retard the formation of stable foams. Silicones and organicpolymers are typical anti-foam agents. For example, polysiloxanes, suchas silicon oil or polydimethyl siloxane, provide antifoam properties.Anti-foam agents are commercially available and may be used inconventional minor amounts along with other additives such asdemulsifiers; usually the amount of these additives combined is lessthan 1 percent, preferably 0.001 to 0.5 wt %, more preferably 0.001 to0.2 wt %, still more preferably 0.0001 to 0.15 wt % (on an as-receivedbasis) based on the total weight of the lubricating oil composition.

IV.K. Corrosion Inhibitors and Antirust Additives

Antirust additives (or corrosion inhibitors) are additives that protectlubricated metal surfaces against chemical attack by water or othercontaminants. One type of antirust additive is a polar compound thatwets the metal surface preferentially, protecting it with a film of oil.Another type of antirust additive absorbs water by incorporating it in awater-in-oil emulsion so that only the oil touches the surface. Yetanother type of antirust additive chemically adheres to the metal toproduce a non-reactive surface. Examples of suitable additives includezinc dithiophosphates, metal phenolates, basic metal sulfonates, fattyacids and amines. Such additives may be used in an amount of 0.01 to 5wt %, preferably 0.01 to 1.5 wt % on an as-received basis.

In addition to the ZDDP anti-wear additives which are essentialcomponents of the present disclosure, other anti-wear additives can bepresent, including zinc dithiocarbamates, molybdenumdialkyldithiophosphates, molybdenum dithiocarbamates, other organomolybdenum-nitrogen complexes, sulfurized olefins, etc.

The term “organo molybdenum-nitrogen complexes” embraces the organomolybdenum-nitrogen complexes described in U.S. Pat. No. 4,889,647. Thecomplexes are reaction products of a fatty oil, diethanolamine and amolybdenum source. Specific chemical structures have not been assignedto the complexes. U.S. Pat. No. 4,889,647 reports an infrared spectrumfor a typical reaction product of that disclosure; the spectrumidentifies an ester carbonyl band at 1740 cm⁻¹ and an amide carbonylband at 1620 cm⁻¹. The fatty oils are glyceryl esters of higher fattyacids containing at least 12 carbon atoms up to 22 carbon atoms or more.The molybdenum source is an oxygen-containing compound such as ammoniummolybdates, molybdenum oxides and mixtures.

Other organo molybdenum complexes which can be used in the presentdisclosure are tri-nuclear molybdenum-sulfur compounds described in EP1,040,115 and WO 99/31113 and the molybdenum complexes described in U.S.Pat. No. 4,978,464.

In the above detailed description, the specific embodiments of thisdisclosure have been described in connection with its preferredembodiments. However, to the extent that the above description isspecific to a particular embodiment or a particular use of thisdisclosure, this is intended to be illustrative only and merely providesa concise description of the exemplary embodiments. Accordingly, thedisclosure is not limited to the specific embodiments described above,but rather, the disclosure includes all alternatives, modifications, andequivalents falling within the true scope of the appended claims.Various modifications and variations of this disclosure will be obviousto a worker skilled in the art and it is to be understood that suchmodifications and variations are to be included within the purview ofthis application and the spirit and scope of the claims.

EXAMPLES General Methods

The lube properties of the products produced in Examples 1 and 2 wereevaluated as provided. The kinematic viscosity (KV) of the products wasmeasured using ASTM standard D-445 and reported at temperatures of 100°C. (KV100) or 40° C. (KV40). The viscosity index (VI) was measuredaccording to ASTM standard D-2270 using the measured kinematicviscosities for each product. The Noack volatility of the products wasmeasured according to ASTM standard D-5800. The pour point of theproducts was measured according to ASTM standard D-5950. The rotatingpressure vessel oxidation test (RPVOT) break time was measured accordingto ASTM standard ASTM D-2272.

In the present and following examples, unless otherwise stated, the C₂₀uPAO dimer used was an approximate mixture of vinylidenes andtrisubstituted olefins at a weight ratio of vinylidenes totrisubstituted olefins in the range from 20/80 to 60/40. The C20 uPAOdimer was prepared according to the method described in Example 1 ofU.S. Patent Publication No. 2013/0090277 A1, the entirety of which isincorporated herein by reference. Thus, the C20 uPAO dimers would takethe following predominant forms:

Example 1—Acid Catalyzed Synthesis of Product I Containing Compound-ICorresponding in Structure to Formula (F-I)

Anisole was alkylated with a C₂₀ uPAO dimer by acid catalyst as shownbelow in Scheme 1 to form Product I containing Compound-I.

A glass round bottom flask under N₂ atmosphere was charged with anisole(83 g, 0.75 mol) (obtained from Sigma-Aldrich) and MCM-49 catalyst (4.52g, 1.5 wt %) to form a mixture. MCM-49 was prepared according to themethods described in U.S. Pat. No. 5,236,575, the entirety of which isincorporated herein by reference. The mixture was stirred and heated to150° C. The C20 uPAO (210 g, 0.75 mol) was added dropwise over a 2 hourperiod. The reaction continued for an additional 2 hours. The reactionmixture was filtered through a bed of Celite to remove solid catalyst.The filtrate was treated with 0.5 wt % or carbon and subjected todistillation up to 210° C. and 5-10 torr to remove unreacted anisole andolefin. The pot bottoms were filtered through a bed of Celite to removecarbon and the filtrate was collected as Product I. The lube propertiesof Product I were determined as provided above and are shown below inTABLE IV.

TABLE IV Lube Properties KV100 (cSt) 4.68 KV40 (cSt) 27.9 VI 74 Noackvolatility (%) 13.3 Pour Point (° C.) −60 RPVOT (minutes) 327

The ¹H NMR and ¹³C NMR spectra of Product I were determined and areshown in FIGS. 1 and 2, respectively. Both ¹³C NMR and ¹H NMR dataindicate that Product I contains nearly exclusively a monoalkylatedproduct. The monoalkylated product nearly exclusively exists as singleisomer (Compound-I), where the benzene ring bonds to a tertiary carbonatom on the alkyl group.

Further, a gas chromatography (GC) analysis was performed on Product I,and a GC spectra for Product I was determined as shown in FIG. 3. The GCspectra for Product I shows a predominantly single peak at 7.9 minutesrepresenting a single product isomer. Smaller peaks between 8 and 10minutes represent unhydrogenated dimerized C20 dimer. The small peak at10.5 minutes represents dialkylated anisole.

Example 2: Acid Catalyzed Synthesis of Product II ContainingCompounds-II Corresponding in Structure to Formula (F-I)

The same preparation as Example 1 was followed except for the use of USYcatalyst instead of MCM-49 to form Product II containing Compounds-II asshown below in Scheme 2.

The lube properties of Product II were determined as provided above andis shown below in TABLE V.

TABLE V Lube Properties KV100 (cSt) 4.42 KV40 (cSt) 25.2 VI 73 Noackvolatility (%) 15.1 Pour Point (° C.) −63 RPVOT (minutes) 332

The ¹H NMR and ¹³C NMR spectra of Product II were determined and areshown in FIGS. 4 and 5, respectively.

GC analysis was performed on Product II, and a GC spectra for Product IIwas determined as shown in FIG. 6. The GC spectra for Product II shows apredominantly monoalkylated product (at 7-8 minute). The monalkylatedproduct exists as a multitude of isomers. The predominant GC peak andmolecule isomer at 7.9 minutes is the same as the peak and moleculeisomer for Product I. The small peak at 5.5 minutes is trace unreactedC20 PAO olefin.

Example 3—Comparison of Base Stock Properties

Various properties of Product I were compared to commercially availablebase stocks, Synesstic™ 5 and Esterex™ NP343 (both available fromExxonMobil Chemical Company, 27111 Springwoods Village Parkway, Spring,Tex. 77389, U.S.A.) as shown in TABLE VI below.

TABLE VI Esterex ™ Property UNIT Test Method Synesstic ™ 5 Product INP343 Appearance None Visual Bright & Bright & Clear Bright & ClearClear Refractive Index @ 25° C. None ASTM D1218 1.5220 1.486046 1.4521Bromine Number g(Br)/100 g ASTM D1159 0.33 1.08 0 (mod) Color, Pt—CoNone ASTM D1500 225 0.5 <1.0 Specific Gravity @ 15.6° C. None ASTM D40520.910 0.893 0.948 Total Acid Number mg KOH/g ASTM D974 0.01 0.004 0.02(mod) Water ppm ASTM D6304 11 124 23.45 Cold Crank Simulator (CCS)Viscosity cP ASTM D5293 5,243 3,900 1,183 @−30° C. CCS Viscosity @−35°C. cP ASTM D5293 10,668 7,459 2,096 Mini Rotary Viscometer (MRV) cP ASTMD4684 13,568 8,717 2,286 Viscosity @−35° C. MRV Viscosity @−40° C cPASTM D4684 — 19,358 4,289 Brookfield Viscosity @ −40° C. cP ASTM D298370,802 19,996 — Brookfield Viscosity @ −26° C. cP ASTM D2983 3,950 2,586900 Pour Point ° C. ASTM D5950 −39 −60 −51 Noack Volatility wt % ASTMD5800 10.5 13.28 2.7 Kinematic Viscosity @ 100° C. cSt ASTM D445 4.774.681 4.31 Kinematic Viscosity @ 40° C. cSt ASTM D445 28.4 27.86 19.2Kinematic Viscosity @ −40° C. cSt ASTM D445 43600 15411(ASTM D7042 3894Anton Parr) Viscosity Index None ASTM D2270 79 74 136 RPVOT Neat minutesASTM D2272 285 327 78.5 Density Correction Factor (g/cm³)/° C. ASTMD1250 0.000527 0.000660 0.000702 Solubility parameter, calculated (d(i)@ (cal/cc){circumflex over ( )}½ via Fedors 8.9 8.67 9.1 25° C.)Correlation Dielectric Strength kv ASTM D877 49.0 22.5 58.1Kauri-Butanol Value None ASTM D1133 31.0 28.5 62.5 4-Ball Wear (scardiameter) mm ASTM D4172 0.68 0.61 0.65 Aniline Point ° C. ASTM D611 27.926.4 23.5 Evaporation Loss @ 205° C. for wt % ASTM D972 15.6 75.9 5.06.5 hour Hydrolytic Stability, total acid number mg KOH/g ASTM D26190.02 0.02 0.20 (TAN) Change Fire Point, Cleveland Open-Cup (COC) ° C.ASTM D92 256 257 291 Flash Point, Pensky-Martens Closed ° C. ASTM D93192 227 245 Cup (PMCC) Flash Point, COC ° C. ASTM D92 222 231 265

As shown in TABLE VI, Product I has better oxidative stability (RPVOT)than Synesstic™ 5 and Esterex™ NP343. Product I has similar viscosity(KV100) as Synesstic^(T)M 5, but improved low temperature properties(pour point, CCS, MRV, Brookfield, KV @ −40° C.). Product I also has alower aniline point than Synesstic™ 5, indicating higher polarity and ageneral improvement in solubilizing strength with regard to additivesand deposits. Further, Product I has better hydrolytic stability thanEsterex™ NP343. Also, the high polarity of esters (e.g., Esterex™ NP343)often causes incompatibility with seals in automotive engines orindustrial equipment.

Example 4—Stribeck and Traction Analysis for Product I, Synesstic™ 5 andEsterex™ NP343

Traction curves for Product I, Synesstic™ 5, and Esterex™ NP343 weredeveloped using a rolling ball on disk method. Each base stock wasexamined under slide to roll ratios (SRR) of 0-70% with a mean speed of2.0 m/s and at three different temperatures (40, 80, 120° C.). TheStribeck curve was developed with a SRR of 50%, a mean speed of 0.007 to3.0 m/s and at three different temperatures (40° C., 80° C., 120° C.).The traction curves for Product I, Synesstic™ 5, and Esterex™ NP343 areshown in FIGS. 7a, 8a, and 9a , respectively, the Stribeck curves forProduct I, Synesstic™ 5, and Esterex™ NP343 are shown in FIGS. 7b, 8b,and 9b , respectively. These data show Product I has a lower coefficientof friction than Synesstic™ 5, which represents improved energyefficiency.

Example 5—Oil Formulations Comparisons Example 5a: Industrial OilFormulations

Three industrial oil formulations of viscosity weight ISO VG 320(Formulations 1-3) were prepared as shown in TABLE VII below. Theformulations contained the same Group IV primary base stocks (obtainedfrom ExxonMobil Chemical Company) and additives (obtained from ElcoCorporation having an address at 1000 Belt Line Avenue, Cleveland, Ohio44109-2848 U.S.A.). Each formulation also included 10 wt % of differentGroup V components, namely Synesstic™ 5, Product I and Esterex™ NP343.

TABLE VII Formulation No. 1 2 3 Components (wt %) SpectraSyn ™ 6 (31cSt) 25.42 25.60 23.92 SpectraSyn Elite ™ 150 (1645 cSt) 63.08 62.9064.58 Synesstic ™ 5 (28.4 cSt) 10.0 Product I (27.86 cSt) 10.0 Esterex ™NP343 (19.2) 10.0 Elco 393D (42) 1.5 1.5 1.5 Total 100.0 100.0 100.0Properties Measurement Protocol 1 2 3 KV40, cSt ASTM D445 318.8 318.9320.1 KV100, cSt ASTM D445 40.69 40.57 41.84 Viscosity Index (VI) ASTMD2270 182 181 186 Pour Point, ° C. ASTM D5950 −54 −54 −54 Brookfield @−26° C., cP ASTM D2983 33,960 33,120 32,640 Brookfield @ −40° C., cPASTM D2983 295,000 238,000 240,000 Foam Seq I ASTM D892 650/285 550/130550/10 Foam Seq II 60/0 20/0 5/0 Foam Seq III 560/100 450/10 70/0 RPVOT,minutes ASTM D2272 368 409 371 4-Ball Wear, mm ASTM D4172 0.50 0.48 0.49Taper Rolling Bearing Relative Viscosity Loss, % at 20 hours 0.5 0.5 0.2(CEC -L45-A-99) Relative Viscosity Loss, % at 100 hours −1.6 −1.7 0.0

Base stocks containing aromatic groups are known to contribute to poorfoaming performance. However, Formulation 2 containing Product I hadbetter foam performance compared to the formulation containingSynesstic™ 5. Further, Formulation 2 containing Product I displayedsuperior oxidative stability (RPVOT).

Example 5b: Automotive Gear Oil Formulations

Three different automotive gear oil formulations of viscosity grade80W90 (Formulations 4-6) were prepared as shown in TABLE VIII below. Theprimary base stocks (Group II/IV) (obtained from ExxonMobil ChemicalCompany) and additives (HiTEC® 385, obtained from Afton ChemicalCorporation having an address at 500 Spring Street, Richmond, Va. 23219,U.S.A.) were incorporated. Each of the three formulations utilized adifferent Group V material at a 10 wt % treat rate.

TABLE VIII Formulation No. 4 5 6 Components (wt %) EHC 50 GRP II (5.4cSt) 50.8 50.6 50.1 SpectraSyn Elite 150 (157 cSt) 31.7 31.9 32.4Synesstic ™ 5 (4.773 cSt) 10.0 Product I (4.681 cSt) 10.0 Esterex ™NP343 (4.4 cSt) 10.0 HiTEC ® 385 (15.93 cSt) 7.5 7.5 7.5 Total 100.0100.0 100.0 KV40, cSt ASTM D445 99.98 100.5 95.17 KV100, cSt ASTM D44514.75 14.89 14.67 VI ASTM D2270 154 155 161 Pour Point, ° C ASTM D5950−24 −27 −24 Brookfield @−26° C., cP ASTM D2983 19,560 20,160 19,650Brookfield @−40° C., cP ASTM D2983 1,620,000 741,000 360,000 Appearancevisual B&C B&C B&C Foam Seq I ASTM D892 550/20 550/20 550/5 Foam Seq II55/0 80/0 80/0 Foam Seq III 390/5 350/10 530/70 RPVOT, minutes ASTMD2272 95 112 124 4-Ball Wear, mm ASTM D4172 0.74 0.80 0.57 Taper RollingBearing Relative Viscosity Loss, % at 20 hours 0.6 0.1 0.0 (CEC-L45-A-99) Relative Viscosity Loss, % at 100 hours 0.5 0.7 0.4

Formulation 5 containing Product I demonstrated better low temperatureperformance (Brookfield @−40° C.) than Formulation 4 containingSynesstic™ 5.

Example 5c: Engine Oil Formulations

Engine oil formulations of viscosity grade 5W30 and 10W30 containing 10wt % of Product I as a co-base stock (Formulation Nos. 7-9) wereprepared as shown in TABLE IX below. The formulations use either a GroupIII (Yubase® 4 commercially available form SK Lubricants Co., Ltd.having an address at 26, Jongro, Jongro-Gu, Seoul 110-728, Korea) orGroup IV (SpectraSyn™ 4) base stock as the primary base stock. The basestock SpectraSyn Elite™ 150 is also a Group IV base stock availablecommercially from ExxonMobil Chemical Company. The additive InfineumP6003™ is commercially available from Infineum USA L.P., Linden Businessand Technology Centre, 1900 East Linden Avenue, P.O. Box 735. Linden,N.J. 07036, U.S.A.

TABLE IX Formulation No. 7 8 9 10 11 12 13 14 Components Yubase ® —70.70 60.70 60.70 60.70 (wt %) 4 (4.237 cSt) SpectraSyn ™ 70.00 60.0060.00 60.00 — 4 (4.144 cSt) Synesstic ™ 10.00 10.00 5 (4.773 cSt)Product I 10.00 10.00 (4.681 cSt) Esterex ™ 10.00 10.00 NP343 (4.4 cSt)SpectraSyn Elite ™ 18.00 18.00 18.00 18.00 17.30 17.30 17.30 17.30 150(157 cSt) Infineum P6003 ™ 12.00 12.00 12.00 12.00 12.00 12.00 12.0012.00 (146.1 cSt) Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00100.00 Viscosity Grade 5W30 5W30 5W30 5W30 10W30 10W30 10W30 5W30 KV40,cSt 60.78 61.49 61.71 58.32 60.31 61.89 61.92 58.44 KV100, cSt 10.5610.62 10.62 10.39 10.39 10.55 10.54 10.31 VI 165 164 163 169 162 161 161166 Pour Point, ° C. −60 −66 −66 −66 −24 −30 −27 −27 CCS @ −25° C., cP —— — — 3769 3,835 3,806 — CCS @ −30° C., cP 4834 4,886 4,906 4,333 6769 —— 5,902 MRV @ −30° C., cP 5014 — — — 22294 13,369 15,057 — MRV @ −35°C., cP 8723 10,782 10,629 9,362 36075 — — 44,390 HTHS @ 150° C., cP3.365 3.395 3.394 3.388 3.373 3.419 3.389 3.460 NOACK @ 250° C., %weight loss 9.8 9.2 10.2 9.1 11.6 11.4 12.8 10.7

As shown in TABLE IX, Product I has similar viscometric performance inengine oil lubricants as Synesstic™ 5.

All patents and patent applications, test procedures (such as ASTMmethods, UL methods, and the like), and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with this disclosure and for all jurisdictions in whichsuch incorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.While the illustrative embodiments of the disclosure have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of thedisclosure. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present disclosure,including all features which would be treated as equivalents thereof bythose skilled in the art to which the disclosure pertains.

The present disclosure has been described above with reference tonumerous embodiments and specific examples. Many variations will suggestthemselves to those skilled in this art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims.

What is claimed is:
 1. A process for making a compound of the followingformula (F-I):

wherein: R¹ is a C₆-C₅₀₀₀ alkyl group; R² is a C₄-C₅₀₀₀ alkyl group; R³at each occurrence is independently hydrogen or a C₁-C₅₀₀ alkyl group;R⁴ is a C₁-C₅₀ alkyl group or an unsubstituted or substituted phenylgroup; R⁵ is hydrogen or a C₁-C₃₀ alkyl group; n is 1, 2, 3, or 4; andm+n is 5; comprising: reacting a compound having the following formula(F-Ia):

with an olefin-containing material comprising a compound having thefollowing formula (F-Ib):

in the presence of an acid catalyst.
 2. The process of claim 1, whereinthe olefin-containing material comprises at least about 75 wt% of thecompound of formula (F-Ib) where R³ is hydrogen.
 3. The process of claim1, wherein the olefin-containing material comprises at least about 50wt% of the compound of formula (F-Ib) where R³ is a C₁-C₁₀₀ alkyl group.4. The process of claim 1, wherein the olefin-containing materialcomprises a mixture of: (i) about 1.0 to about 99 wt% of the compound offormula (F-Ib) where R³ is hydrogen; and (ii) about 1.0 to about 99 wt%of the compound of formula (F-Ib) where R³ is a C₁-C₁₀₀ alkyl group. 5.The process of claim 1, wherein the olefin-containing material has anisotacticity of at least about 60 mol%.
 6. The process of claim 1,wherein the acid catalyst is a solid acid catalyst selected from thegroup consisting of a solid Lewis acid, an acid clay, a polymeric acidicresin, silica-alumina, a mineral acid and a combination thereof.
 7. Theprocess of claim 1, wherein the acid catalyst comprises one or moremolecular sieve having a framework structure selected from the groupconsisting of BEA, EUO, FAU, FER, HEU, MEL, MFI, MOR, MRE, MTW, MTT,MWW, OFF, and combinations thereof.
 8. The process of claim 7, whereinthe molecular sieve is selected from the group consisting of ZSM-5,ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-48, ZSM-50, Zeolite Beta, MCM-56,MCM-22, MCM-36, MCM-49, zeolite Y, zeolite X, and combinations thereof.9. The process of claim 1, wherein at least about 50 mol% of thecompounds produced have the moiety comprising R¹, R², and R³ bonded tothe phenyl ring at a position para to the —O—R⁴ moiety.
 10. A lubricantbase stock comprising one or more of the compound of the followingformula (F-I):

wherein: R¹ is a C₆-C₅₀₀₀ alkyl group; R² is a C₄-C₅₀₀₀ alkyl group; R³at each occurrence is independently hydrogen or a C₁-C₅₀₀ alkyl group;R⁴ is a C₁-C₅₀ alkyl group or an unsubstituted or substituted phenylgroup; R⁵ is hydrogen or a C₁-C₃₀ alkyl group; n is 1, 2, 3, or 4; andm+n is 5; wherein the lubricant base stock has one or more of: (i) ahydrolytic stability, measured according to ASTM D-2619, of about 0.01to about 1.0 mg KOH/g; (ii) a solubility of measured according to FedorsCorrelation, of about 8 to about 10 d(i) at 25° C. (cal/cc){circumflexover ( )}1/2; and (iii) a rotating pressure vessel oxidation test(RPVOT) break time, measured according to ASTM D-2272, of at least about200 minutes.
 11. A formulated lubricant composition comprising one ormore of the lubricant base stocks of claim 10 in an amount from about 5wt% to about 90 wt%, based on the total weight of the formulatedlubricant composition.